CN112316927B - Water treatment agent capable of rapidly adsorbing methylene blue and preparation method thereof - Google Patents
Water treatment agent capable of rapidly adsorbing methylene blue and preparation method thereof Download PDFInfo
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- CN112316927B CN112316927B CN202011254043.4A CN202011254043A CN112316927B CN 112316927 B CN112316927 B CN 112316927B CN 202011254043 A CN202011254043 A CN 202011254043A CN 112316927 B CN112316927 B CN 112316927B
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- adsorbent
- methylene blue
- carbon nano
- glycidyl ether
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The technical scheme includes that functional carbon nano tubes and magnetic nano particles are dispersed in ethanol, the magnetic nano particles are assembled on the surfaces of the functional carbon nano tubes by means of ultrasound, the obtained solid product is subjected to drying and grinding after the ultrasound is finished, then the solid product is dispersed in an organic solvent, polymerizable glycidyl ether, acrylonitrile and an initiator are added, nitrogen is filled to replace air in a bottle, the air is stirred in an oil bath pot at 60-70 ℃ for 2-3 hours, the solvent is removed after the reaction is finished, and the solid product is dried in vacuum, so that the adsorbent is obtained. According to the invention, the carbon nano tube, the acrylonitrile and the polymerizable glycidyl ether are used as raw materials to prepare the modified carbon nano tube/polyacrylonitrile composite material which is used as a methylene blue rapid adsorbent, so that the adsorption capacity of the modified carbon nano tube/polyacrylonitrile composite material to the methylene blue is large, and the adsorption time is short; in addition, after the methylene blue is adsorbed, the adsorbent can be recovered through an externally applied magnetic field, so that secondary pollution caused by the residual adsorbent in the water body can be prevented.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a water treatment agent capable of rapidly adsorbing methylene blue and a preparation method thereof.
Background
Methylene blue is a phenothiazine salt, and is widely applied to chemical indicators, dyes, biological colorants and the like, and has good curative effects on preventing and treating saprolegniasis, ichthyophthiriasis and the like of freshwater fish, so that the methylene blue can be also applied to aquaculture. However, the use of methylene blue in large quantities can produce certain toxic and side effects on the cultured aquatic organisms, accumulate a certain amount of residues in the aquatic organisms through biological enrichment, and cause new hidden hazards to the life safety of fish. However, the current common adsorbents for methylene blue are mostly wastewater treatment agents used in dye wastewater, and have low adsorption speed and long adsorption time.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the adsorbent capable of rapidly adsorbing the residual methylene blue in the water body.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a process for preparing the adsorbent for quickly adsorbing methylene blue includes such steps as dispersing functional carbon nanotubes and magnetic nanoparticles in alcohol, ultrasonic assembling the magnetic nanoparticles on the surface of functional carbon nanotubes, centrifugal separation, drying, grinding, dispersing in organic solvent, adding polymerizable glycidyl ether, acrylonitrile and trigger, filling nitrogen gas, displacing air in bottle, stirring in oil bath at 60-70 deg.C for 2-3 hr, vacuum distilling to remove solvent, and vacuum drying.
Further, the functional carbon nanotubes are hydroxylated carbon nanotubes or aminated carbon nanotubes.
Further, the magnetic nanoparticles are oleic acid modified ferroferric oxide magnetic nanoparticles.
Further, the polymerizable glycidyl ether is selected from one of allyl glycidyl ether, glycidyl methacrylate, and 4-hydroxybutyl glycidyl acrylate.
Further, the organic solvent is one of N, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane or dimethyl sulfoxide.
Further, the initiator is azobisisobutyronitrile or benzoyl peroxide.
Further, the mass ratio of the functional carbon nano tube to the magnetic nano particles is 1:0.05-0.2, and the concentration of the functional carbon nano tube is 0.1g/ml.
Further, the molar ratio of the polymerizable glycidyl ether to the acrylonitrile to the initiator is 1:1:0.01, and the mass ratio of the acrylonitrile to the functional carbon nano tube is 0.5-1.5:1.
An adsorbent for rapidly adsorbing methylene blue prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that: the invention takes carbon nano tube, acrylonitrile and polymerizable glycidyl ether as raw materials to prepare the methylene blue rapid adsorbent, and firstly, the polyacrylonitrile has the characteristics of excellent chemical stability, good weather resistance, ageing resistance, pollution resistance, easy cleaning and the like; the surface of the carbon nano tube is of a porous structure, has a very large specific surface area and very strong adsorption effect on methylene blue, and the functional carbon nano tube is selected, so that the surface of the functional carbon nano tube is rich in hydroxyl or amino groups, the dispersibility of the carbon nano tube in a polymerization system is effectively improved, and the functional carbon nano tube can be subjected to ring-opening reaction with glycidyl ether; the polymerizable glycidyl ether can be polymerized with acrylonitrile free radicals on one hand and grafted with the functional carbon nano tube on the other hand, so that a modified carbon nano tube/polyacrylonitrile composite material is formed, and the modified carbon nano tube/polyacrylonitrile composite material can rapidly adsorb methyl blue, has large adsorption capacity and short adsorption time, and effectively avoids death of farmed fish caused by methylene blue residues; in addition, the invention is also added with magnetic nano particles, and after the methylene blue is adsorbed, the adsorbent can be recovered by an externally applied magnetic field so as to prevent secondary pollution caused by long-time residue of the adsorbent in the water body.
Description of the drawings:
FIG. 1 is a graph of methylene blue adsorption versus time for examples 1-3.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1:
dispersing 1g of functional carbon nano tube and 50mg of magnetic nano particles in 10ml of ethanol, assembling the magnetic nano particles on the surface of the functional carbon nano tube by ultrasonic, centrifuging for multiple times after the ultrasonic treatment is finished, drying and grinding the obtained solid product, then dispersing the solid product in 10ml of organic solvent, adding 10mmol of polymerizable glycidyl ether, 10mmol of acrylonitrile and 0.1mmol of initiator, filling nitrogen, displacing air in a bottle, stirring and reacting in an oil bath pot at 60-70 ℃ for 2-3h, distilling under reduced pressure to remove the solvent after the reaction is finished, and drying the solid in vacuum to obtain the adsorbent.
Example 2:
dispersing 1g of functional carbon nano tube and 50mg of magnetic nano particles in 10ml of ethanol, assembling the magnetic nano particles on the surface of the functional carbon nano tube by ultrasonic, centrifuging for multiple times after the ultrasonic treatment is finished, drying and grinding the obtained solid product, then dispersing the solid product in 10ml of organic solvent, adding 15mmol of polymerizable glycidyl ether, 15mmol of acrylonitrile and 0.15mmol of initiator, filling nitrogen, displacing air in a bottle, stirring and reacting in an oil bath pot at 60-70 ℃ for 2-3h, removing the solvent by reduced pressure distillation after the reaction is finished, and drying the solid in vacuum to obtain the adsorbent.
Example 3:
dispersing 1g of functional carbon nano tube and 50mg of magnetic nano particles in 10ml of ethanol, assembling the magnetic nano particles on the surface of the functional carbon nano tube by ultrasonic, centrifuging for multiple times after the ultrasonic treatment is finished, drying and grinding the obtained solid product, then dispersing the solid product in 10ml of organic solvent, adding 20mmol of polymerizable glycidyl ether, 20mmol of acrylonitrile and 0.2mmol of initiator, filling nitrogen, displacing air in a bottle, stirring and reacting in an oil bath pot at 60-70 ℃ for 2-3h, distilling under reduced pressure to remove the solvent after the reaction is finished, and drying the solid in vacuum to obtain the adsorbent.
In embodiments 1-3, the functional carbon nanotubes are hydroxylated carbon nanotubes or aminated carbon nanotubes;
the magnetic nano particles are oleic acid modified ferroferric oxide magnetic nano particles;
the polymerizable glycidyl ether is selected from one of allyl glycidyl ether, glycidyl methacrylate and 4-hydroxybutyl glycidyl acrylate;
the organic solvent is one of N, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane or dimethyl sulfoxide;
the initiator is azobisisobutyronitrile or benzoyl peroxide.
The adsorbents prepared in examples 1 to 3 were used for water treatment of cultivation water containing methylene blue, 20mg of the adsorbent was put into 50ml of methylene blue solution with an initial concentration of 100mg/L, and the solution was placed in a shaking table at a constant temperature of 30℃and shaken for a certain period of time, and the absorbance of the solution after adsorption was measured by an ultraviolet spectrophotometer. As shown in FIG. 1, which shows the relationship between the methylene blue adsorption rate and time in examples 1-3, the adsorption rate of the prepared adsorbent can reach 80% in a short time, and the adsorption rate of the adsorbent to the methylene blue can reach more than 95% over time.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (7)
1. The preparation method of the adsorbent for rapidly adsorbing methylene blue is characterized by comprising the following steps of: dispersing functional carbon nano-tubes and magnetic nano-particles in ethanol, assembling the magnetic nano-particles on the surfaces of the functional carbon nano-tubes by ultrasonic, centrifuging for multiple times after ultrasonic treatment, drying and grinding the obtained solid product, dispersing the solid product in an organic solvent, adding polymerizable glycidyl ether, acrylonitrile and an initiator, filling nitrogen gas to replace air in a bottle, stirring and reacting in an oil bath pot at 60-70 ℃ for 2-3 hours, distilling under reduced pressure to remove the solvent after the reaction is finished, and drying the solid in vacuum to obtain the adsorbent; the functional carbon nanotubes are hydroxylated carbon nanotubes or aminated carbon nanotubes; the mass ratio of the functional carbon nano tube to the magnetic nano particles is 1:0.05-0.2, and the concentration of the functional carbon nano tube is 0.1g/ml.
2. The method for preparing the adsorbent for rapidly adsorbing methylene blue according to claim 1, wherein the magnetic nanoparticles are oleic acid modified ferroferric oxide magnetic nanoparticles.
3. The method of preparing a fast methylene blue adsorbent according to claim 1, wherein said polymerizable glycidyl ether is selected from one of allyl glycidyl ether, glycidyl methacrylate, and 4-hydroxybutyl glycidyl acrylate.
4. The method for preparing the adsorbent for rapidly adsorbing methylene blue according to claim 1, wherein said organic solvent is one of N, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane or dimethyl sulfoxide.
5. The method for preparing an adsorbent for rapidly adsorbing methylene blue according to claim 1, wherein said initiator is azobisisobutyronitrile or benzoyl peroxide.
6. The method for preparing the adsorbent for rapidly adsorbing methylene blue according to claim 1, wherein the molar ratio of the polymerizable glycidyl ether to the acrylonitrile to the initiator is 1:1:0.01, and the mass ratio of the acrylonitrile to the functional carbon nano tube is 0.5-1.5:1.
7. An adsorbent for rapidly adsorbing methylene blue produced by the production process according to any one of claims 1 to 6.
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Citations (4)
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CN101735416A (en) * | 2009-12-29 | 2010-06-16 | 浙江大学 | Method for preparing water-soluble cross-linked polymer grafted carbon nano tube |
CN102553532A (en) * | 2012-01-17 | 2012-07-11 | 同济大学 | Method for preparing magnetic carbon nano-tube adsorbent having high adsorption capacity and used for removing dye from aqueous phase |
CN106076271A (en) * | 2016-06-27 | 2016-11-09 | 济南大学 | A kind of preparation method and application of nano-magnetic polylysine/(graphene carbon nanotube) biological adsorption material |
CN111495319A (en) * | 2020-04-24 | 2020-08-07 | 匡秋茂 | Hyperbranched polymer-based magnetic porous carbon adsorption material and preparation method thereof |
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US20160243523A1 (en) * | 2013-09-30 | 2016-08-25 | Council Of Scientific & Industrial Research | Magnetic nanoparticles decorated activated carbon nanocomposites for purification of water |
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Patent Citations (4)
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CN101735416A (en) * | 2009-12-29 | 2010-06-16 | 浙江大学 | Method for preparing water-soluble cross-linked polymer grafted carbon nano tube |
CN102553532A (en) * | 2012-01-17 | 2012-07-11 | 同济大学 | Method for preparing magnetic carbon nano-tube adsorbent having high adsorption capacity and used for removing dye from aqueous phase |
CN106076271A (en) * | 2016-06-27 | 2016-11-09 | 济南大学 | A kind of preparation method and application of nano-magnetic polylysine/(graphene carbon nanotube) biological adsorption material |
CN111495319A (en) * | 2020-04-24 | 2020-08-07 | 匡秋茂 | Hyperbranched polymer-based magnetic porous carbon adsorption material and preparation method thereof |
Non-Patent Citations (1)
Title |
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